Interpolymers of vinyl chloride, alkyl acrylate, and styrene



Patented July 29, 1952 v INTERPOLYMERS OF VINYL CHLORIDE,

ALKYL ACRYLATE, AND ST YRENE Robert J. Wolf and Anthony A. Nicolay, Cleveland, hio,'assignors to The B.F. Goodrich Company, New York, N. Y., a corporation of New York No Drawing. Application May 20, 1950, Serial No. 163,335

Claims. (Cl. 260-805) V The present invention relates to interpolymers obtained by the polymerization of monomeric mixtures containing at least three monomeric components, each in particular proportion, one of which is vinyl chloride, another of which is styrene, and the third of which is an alkyl acrylate particularly an octyl acrylate.

The copolymers of vinyl chloride and the alkyl acrylat es are well knownto the art. The copolymers of vinyl chloride and styrene, on the other hand, have not been so known, nor have they been used to any great extent. The reason lies in the inherent difliculty in achieving a true copolymerization reaction between the latter two monomers. Attempts to copolymerize vinyl chloride and styrene have always resulted in a hard, brittle, relatively useless material which even when plasticized cannot be formed into clear plastic sheets or molded articles because of the presence therein of polyvinyl chloride and polystyrene which are incompatible with each other. In the copending application of Harold Tucker, Serial No. 84,751, filed March 31, 1949, it is disclosed that the copolymerization of vinyl chloride and styrene by usual methods results in a mixture of polyvinyl chloride, polystyrene, and perhaps some vinyl chloride styrene copolymer and that only by careful and exacting technique,

comprising proportional addition of vinyl chloride and styrene to a reaction medium containing certain powerful catalysts is it possible to obtain a true copolymer free of polyvinyl chloride and polystyrene. The vinyl chloridestyrene copolymer thus obtained, however, requires the addition of plasticizer for use in most processing opera tions.

We have now discovered that the usual difiiculties attendant on achieving copolymerization between vinyl chloride and styrene may be eliminated and excellent interpolymers containing interpolymerized vinyl chloride and styrene (that is, free from polyvinyl chloride and polystvrene) obtained without the use of special techniques if one or more alkyl acrylates are added to the monomeric mixture of vinyl chloride and styrene before or during polymerization. The presence of the third monomer, an alkyl acrylate, causes a smooth reaction to occur, in which vinyl chloride, styrene, and the alkyl acrylate combine to form interpolymers having new and unique properties quite unlike the properties of the copolymers of any two-monomers of the'mixture.

Other monoolefinic monomeric materials may also be present in the monomeric mixture, along with the vinyl chloride, styrene, and alkyl acrylate. Such monomers include, for example, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, vinyl benzoate, alkyl esters of an alpha-alkyl acrylic acid such as methyl methacrylate, isobutylene and others. One or more of these other monomeric materials may :be utilized in amounts totalling up to 10%"0f the monomeric mixture. However, since the tripolymersmade from mixtures containing only vinyl chloride, styrene and an alkyl a'crylate are superior in clarity and strength to the multipolymers containing one or more of the above additional monomers, it is'preferred that only the threespecified types of monomers be present in the reaction mixture. 1

The relative proportions of monomers, which are employed in the production of our interpolymers are somewhat critical since desirable'prop erties are not secured withthe three types-Jot monomers in any proportion, but the proportions may vary within certain limits. In the monomeric mixture we have found it necessary-to employ from 35 to 90% by weight of vinyl chloride, from 5 to by weight of the alkyl acry late, and from 5 to 50% by weight of styrenewith at least 90% by weight of the monomeric mixtures made up of these three specified ingredients; particularly valuable are those'interpolymers made from monomeric mixtures consisting of from O'to by'weight of vinyl chloride, from 10 to 50% of the alkyl acrylate, and from 5 to 35% styrene.

Any of the alkyl esters of acrylic acid maybe employed as the third component of the monomeric mixture. Among these are methyl," ethyl, 'propyl, butyl, amyl, hexyl, heptyl, octyL 'nOnyl, isononyl, decyl, and even higher alkyl acrylates. We have found that the acrylates particularly preferred are the higher alkyl acrylates in which the alkyl group contains from five toten carbon atoms, the members of this classforming particularly valuable interpolymers with vinyl chloride and styrene all of which are processable without the addition of plasticizers even though they range from soft and flexible materials to materials which are relatively hard and stiff. We have found that the degree of plasticity or inherent processability imparted to our new interpolymers by the higher alkyl acrylates is largely determined by the length and configuration of the alkyl group in the alkyl acrylate and that this finding corresponds roughly with the observed degree of plasticization imparted to ordinary vinyl resins by extraneous addition of ester 55 type plasticizer containing similar alkyl'groups.

For example, di-2-ethylhexyl phthalate is an excellent plasticizer for vinyl chloride polymers, and 2-ethylhexyl acrylate has been found to impart an excellent degree of inherent processability to its interpolymers'with vinyl chlorideand styrene. Illustrative higher alkylzacrylates 'Withinthe preferred class utilizable in this invention include n-amyl acrylate, n-hexyl acrylate, the isohexyl acrylates, n-heptyl aorylate, isoheptyl acrylates, capryl acrylate (l-methyl heptylqacrylate) noctyl acrylate, the isooctyl acrylates such as 6-methyl heptyl acrylate, .nenonyl acrylate, the isononyl acrylates such as 3;5;5-,trimethyl-hexyl acrylate, n-decyl acrylate, and:others.

It is especially preferred to employ higher alkyl acrylates in which the alkyl group.co ntains a total of 8 to 10 carbon atoms, and possesses "a carbon chain of from 6 to 10 atoms. Compounds within this class are G-methyl heptyl'acrylate (isooctyl acrylate) 3,5,5-trimethylhexyl acrylate, .Zieethylhexyh acrylate, ;cap ryl acrylate (lmethyl :heptyl :acrylate), :;n+octyl ;acrylate and others.

'JTheshigher alkyliacrylatesqof thisclass have been ifoundttozimpartithe greatest'ease of processing :andrgreatestzsoftness :and flexibility to our new interpolymers; :neoctylracrylate being the =-most rprofioient: acrylate in;this respect.

iiheizpolymerizationzof our new interpolymers #may bezcarried out-inany conventional-manner,

although-polymerizationz in aqueous emulsion is --oficourseiessential when a latex of' the-interpolyanernisnthe? desired end; product. In addition to 'this preferredzmethod, thezmixt-ure of monomers :be: rpolymerized in solution a in a suitable solvent for the monomer, ;or;in thexabsence of r zsolventzorzdiluent. interpolymers in the form -ofzfineaeranules; arma-lsorsecureid: by theso -called ifpeari?frtypezpolymerization; method .in which the imonomersxare rpolymerized -in aqueous suspenzsion'amthe lpresence rofza1colloidal: materialv such ;-as.=tgelatin; bentonite clay polyvinyl alcohol, polyoacrylicsacid; or the; like. .iIrrespectivec of theimethod; of i polymerization employed; the catalystmay be any .of the catarlyststoommonlyemployedtfor the polymerization --ofrvinylc.and-rvinylidene compounds. Actinic radiationI-mayabe employed,.as well as-lthe various peroX-Xsen: compounds such as hydrogen: peroxzidepbenzoyl peroxide; 0,0 -dichlorobenzoylperoxidemcaproyl -rperoxide, caprylyljDemxide, pelarrgm ylgperoxide, cumene -hydroperoxide, tertiary butyl di-perphthalate, tertiary butyleperbenzoate, :sodium, potassium and -.-.ammoni..um' :persulfate, sodium gperborate, sodium :percarbonate, -and others:

mThe above class-:of icatalysts are-greatly ac- .tivatedewhenusedrim-combination with a reduceingflsubstanceTsuch -as sodium'thiosulfate, sodium sulfite,-a-polyhydroxy phenol; etc.,- inwhat. is commonly referred tov-asra 1 fRedox polymerization. .Both-ithe peroxygen compounds and their Redox combinations with various'reducing substances .arezalso;greatly-activated by the=presence of a esmallfamountpfja soluble,- heavy metal salt such as'silver nitrate,coppersulfate, ferric and cobalt compounds. andr-many others.

.--In some:instancesitlmay be desirable torcontrol-or-adjust the hydrogen ion concentration of xthe'reactionz mixture,- which tends .to become more iacid-because of-liberation.of;I-ICl during the poly- ;merization. -Itis generally preferred, therefore, "that;ai-bufferingagent be-added to the reaction -mixture. :For this. -purpose sodium bicarbonate,

.sodium carbonate; ammonium bicarbonate, am-

.monium-hydroxide; sodium hydroxide,the;amino- .octadecane-l sulfonic acid, etc.; 'fonates such as sodium alkyl benzene sulfonates,

such in coating, processes-,and in the casting of 1 unsupported .film.

:iniaqueous emulsion. Ordinary soaps-such as the alkali metal, .ammonium and alkanolamine salts of fatty acids, including sodium oleate,

--sodium myristate, potassium palmitate, ammonium stearate, ethanol amine laurate, and the like,: as -well".as rosin or dehydrogenated rosin acid -soaps -maybe -employed, but more useful latices aresecured withthe synthetic saponaceous ma- -.terials.includinghymolal sulfates and sulfonates, ;such as sodiumdauryl sulfate, sodium cetyl sulfate, the sodium;-.salt of sulfonated paraffin oil, the sodium salt of dodecane-l-sulfonic acid,

alkaryl sulsodiumjisopropyl naphthalene sulfonate, sodium isobutyl naphthalene sulfonate, and the like; and

alkali; metal, salts of sulfonated ,dicarboxylidacid ,estersand amides such asssodium dioctyLsulfo- .su-ccinate, -sodium-N10ctadecylesulfosuccinamate,

acetic..emulsions .and ordinary fatty acid soaps yield. alkaline 1 emulsions, whereas thev hymolal sulfates an"d-...sulf.onates which. are particularly preferred, may ,be utilized-.inremulsionsover .a

- i-wide p-I-Irange.

.ture at which -the polymerization is carried out ,not critical. It .may-vary widely .from -30 :to. .C'. orl hi her, though .best results are gen- .er'allyobtained, at -a temperature of 3113011130" C. to ,.aboutjC.

.In ,order,to ,minimize variation in the rate of reaction and to ,obtaiagreater homogeneity in .thepro'ducts, it, may esometimesnbe desirable ,to withhold'a portion: or all of one' or more of the monomeric materials, and add the withheld portion iniincrements or continuously ,over the reaction period. An entirely. satisfactory method is to, premixfthe monomeric materials, which in the pure state have little tendency to spontaneously copolymerize, and add small increments of the. mixture oradd the mixture in a continuous manner to the reaction vessel over. the course of the ,reaction. The polymerization in aqueous emulsion also may be'efiectedin the presence of a smallamount of a seedlatex in order to obtain larger 1 latex particles and greater fluidity for given latex solids content. If the amount of the emulsifier -in the aqueous emulsion is carefully controlled .during the .reaction at. somewhat less than ..the amounttheoretically necessary to pro.-

.vide. .a monomolecularfilm of emulsifier onthe latex :particles, the initiation of new particles willbe suppressed,.and-thegrowth of larger particles favored. .Bytheselatter methodsla latex ofthe interpolymers may be produced having high fluidity and over 50% total solids content, properties greatly. desired in. a latex for .use. as impregnating and dipping scope thereof.

Example 1 A tripolymer was prepared by the polymerization of the monomeric materials contained in the reaction mixture having the following proportions:

Material Parts by.

Weight Vinyl Chloride Isooctyl Acrylatc Styrene Potassium Persulfat Emulsifler 1 NH; Water (Distilled) 1 Sodium salt of a sulfonated petroleum fraction known commercially as Duponol 189 S.

The water, emulsifying agent, and potassium persulfate were added to the reaction vessel and the vessel then sealed and evacuated. The ammonia and monomers were'then added and the contents of the reaction vessel heated to 50 C. with constant agitation. In about hours the reaction had reached a yield of about 95%. The product was a stable, very white appearing latex, having a total solids content of 50%.

The latex was coagulated by the salt-acid method, and a fine granular coagulum was obtained. The coagulum was dried at a temperature of Bil-100 C. The dry granular polymer was found to band into a smooth clear sheet on a plastic roll mill, the rolls of which were maintained at only 180 F. without the addition of plasticizer, and'without sticking of the plastic to the rolls. The tripolymer sheet was soft (90 Durometer A at C.) and was very flexible. The sheet, moreover, had a dry feel and was free of tack or stickiness.

The tripolymer of Example 1 was mixed on a plastic roll mill with a 2% by weight of the resin of the mixed barium and cadmium salts of naphthenic acids, and a disc 3" wide and thickness prepared by press molding for one minute at 140 C. at 2000 lbs/sq. in.'pressure. I Thetripolymer was found to fuse readily and flow sufficiently to completely fill the mold and form a completely fused disc having smooth edges. The disc was clear, colorless, and extremely flexible. Determination of the physical properties of the tripolymer performed on a similarly press molded test strip revealed 'a tensile strength of 2000 lbs/sq. in., an elongation of 225%, and a modulus at 100% elongation of 1300 lbs/sq. in.

Example 2 A tripolymer was prepared by polymerizing the monomeric materials in a reaction mixture having the following proportions:

The reaction mixture was agitated at 45 C. for 27 hoursto obtain a yield of of tripolymer.- A portion of the latex was frozen to recover the tripolymer in granular form.

The tripolymer of Example 2 was similar to that of Example 1. It formed water-white sheets when milled without plasticizer using mill roll temperatures of only 170 F. The milled sheet was slightly softer than that of Example 1 (65 Durometer A), had a brittleness temperature of -20 F., and formed a molded disc (when molded one minute at C.) which was completely fused, clear, and very flexible. The tripolymer was very soluble, forming a clear, water-like, high solids solution in tetrahydrofuran.

The'latex'obtained in Example 2, when coated on a clean glass plate and heated for 2 minutes at 0., formed an excellent, clear film which was easily stripped from the plate. The film had a tensile strength of 1950 lbs/sq. in, an elongation of 275%, and a Graves tear strength of 396 lbs/in. The film exhibited excellent heat resistance as shown by the slope of the curve of percent light transmission plotted against time of heating at 150 C. By this method the tripolymer of this Example 2 hada slope of -0.47 as com- Other tripolymer-s were prepared by the polymerization at 50 C. of a mixture consisting of 45% vinyl chloride, 35% 2-ethylhexyl acrylate, and 20% styrene, and of a mixture consisting of 40% vinyl chloride, 30% 2-ethylhexyl acrylate and 30% styrene in a reaction mixture similar, to that of Example 2. The tripolymers were obtained in the form of latices containing in excess of 50% total solids. The solid tripolymers had hardness values, respectively, of 60 and 70A and could be easily molded in 1 minute at 140 C. under 2000 lbs/sq. in. to form completely fused discs or sheets. The light and heat stability of the tripolymers may be shown. by a test consisting of coating a clean glass microscope slide with the polymer, exposing the coating to prolonged heating or to prolonged exposure to ultraviolet light, and measuring the light transmitted through the coating before and after exposure (the ratio of the light transmitted after exposure to that before, expressed in percent being taken as an indication of the stability of the polymer coating). The light stability of the tripolymers after exposure to ultraviolet light for four hours ranged from 90 to 97% and the heat stability after being heated for 2 hrs. at C. in air ranged from '71 to 79%.

The tripolymers of Examples 2'and 3 were used in the form of the latices with the addition of ping and impregnatingapplications.

solids of di-2-ethylhexyl phthalate plasti-' Example-4 'A-tripoly-mer was prepared by the-polymerization of the monomeric --materials contained-in the following reaction mixture:

The reaction was-substantially complete in 35 hoursat 50 C. with constant agitation. The resulting tripolymer latex contained "53.8% total solids, but was fairlyfluid an'd stabl'e'on storage.

The heat stability or per cent light'transmission n of a film cast from .a'tetrahydrofuran solution of the polymer after heating 24' hours at 175 C. in'an air ovenwas 77%, and the light stability or per: cent light transmission after exposure fore hours to .a powerful ultraviolet light Was 89%. The .tripolymerlatex cast onan endless stainless steel belt and dried for three minutes at 150 C. wasclear, smooth and flexible, tack-free, and exceedingly strong. The film was made into transparent or translucent shower curtains, raincoats, umbrellas, etc., which outlasted several similar articles made of plasticized vinyl resin. Because this tripolymer required no plasticizer, the latex or cement cast films did not stifien, even when agitated'for several weeks in-warm soapywater at 180 F.

Example 5 Atripolymer wasprepared by the polymerization of the monomeric .materialsrcontained in the following reaction mixture:

Parts by Materials Weight Vinyl .Ch1oride 75.0 2-Ethylhexyl Acrylate 20.0 Styrene 5. Potassium Bersulfate 0. 'Ernulsifier (same as Example 1) '4. 0 H3 0.2 Water 95. 3

The reaction-was complete in. 36 hours .at 45C. with .the production of .anexcellent medium-particlesize latex. Thelatex formedgoodfilmswhen heated at 100 C.,. andexcellent films. when heated to 1502C.

The .coagulated. tripolymer .of- Example .5 could cent light transmission .after,he.ating.. 24. hoursiat 175 .C. of. 86%.

Easamplefi :A- 'tripolymer. made "from amixture consisting of 80% vinyl chloride, 10%n-octyla acrylate; and 10% styrene'was a relatively hard material (60 Durometer C at 0;) but required mill roll temperatures of only200 F. formilling,-w as;extruded without the addition of.plasticizer'in., an extruder having an unheated;screw,a backecyl- ,indertemperature-of 200 1F. and a dietempera- .ture of 250 F. The warm milled tripolymer sheet was transferred to a four rollcalender havingall four rolls maintained at 250 F. and a smooth,

clear'sheet of 10 mils thickness obtained. .By contrast, plasticized polyvinyl chloride of equivalent hardness is very diflicult to mill, ext-rude or calender, and even much softer forms of plasticized polyvinyl chloride require milling temperaturesof 280 F., extruding temperatures-of 340 to 3,90 F. and calenderin temperatures ofabout 350. F.

Example 7 Atripolymer was preparedby subjecting the following reaction mixture to polymerizing conditions at 50 C.:

Materials Weight Vinyl Chloride 3,5,5-Trimethylhexyl Acryl t Oetadecyl Acrylate. Styrene Potassium Persuliate. {llmulsifier (same as Example 1)..

Water 0 Ha on) mmowoooo Example 8 A tripolymer made from a monomeric mixture consisting of 55% vinyl chloride, 40% 2-ethylhexyl acrylate and 5% styrene (utilizing a reaction recipe similar to that of Example 5) had :a hardness of 66 Durometer A and when tested by the Clash-Berg flexibility test, which measures the temperature at which a sample of polymer composition under torsion exhibits a given degree offlexibility (in this case 135,000 lbs/sq. in. .at Tr), showed a flexibility temperature of -32.5 C. A high-grade polyvinyl chloride plasticized with 50 parts per parts of resin of di-2-ethylhexyl phthalate has. a flexibility temperature gof only-225 C. under the same torsional ,loading.

ExampZe'Q The precedin examples have-.demonstrated the use of the preferred class of higher 'alkyl acrylates, however, the lower alkyl acrylates may also be used With-advantages over vinyl chloride styrene two component polymers. A mixture consistingof 50% by weight vinyl chloride, 40% by weight of ethyl acrylate, and 10% styrene was polymerized in the persulfate catalyzed system of Example 1. A'fluid latex-of 50% total solids content was obtained. A tripolymer was a hard material though it was quite clear and flexible. A mixture consisting of 50% by weight of vinyl chloride, 20% isooctyl acrylate,"20% ethyl acrylate, and 10% styrene .Was similarly polymerized to form a tetrapolymer considerably softer than that made from the 40% ethyl acrylate mixture. Both tripolymers, how ever, were'found capable of being milled without plasticizers-at temperatures of 200to 225 F.

Interpolymers similar to those described in Examples 1 to 8 are obtained when 10% of acrylonitrile or vinylidene chloride is polymerized along with a mixture containing 35 parts vinyl chloride, 55 parts n-octyl acrylate and 10 parts of styrene. However, since the use of most other monomers does not seem t impart additional desirable properties to the interpolymers of this invention, it is of course preferred to produceinterpolymers from monomeric mixtures containing only vinyl chloride, higher alkyl acrylates, and styrene.

While the invention has been described with particular reference to certain preferred embodiments thereof, it is possible to make variations and modifications therein without departing from the spirit and scope of the invention as defined in the appended claims.

We claim:

1. An interpolymer made by polymerizing in aqueous emulsion a mixture of monomeric materials comprising from 35 to 90% by weight of vinyl chloride, from 5 to 60% by Weight of an alkyl acrylate in which the alkyl group contains from 5 to carbon atoms, and from 5 to 50% by weight of styrene.

2. A tripolymer made by polymerizing in aqueous emulsion a mixture of monomeric materials consisting of from 40 to 85% by weight of vinyl chloride, 10 to 50% by weight of alkyl acrylate in which the alkyl group contains a total of 8 to 10 carbon atoms and possesses a carbon chain of 6 to 10 carbon atoms, and from 5 to 35% by weight of styrene.

3. A tripolymer made by polymerizing in aqueous emulsion a monomeric mixture consisting of 10 from to 85% by weight of vinyl chloride, from 10 to by weight of n-octyl acrylate, and from 5 to 35% by weight of styrene.

i. A tripolymer made by polymerizing in aqueous emulsion a mixture of monomeric material consisting of from 40 to by weight of vinyl chloride, from 10 to 50% by Weight of Z-ethylhexyl acrylate, and from 5 to 35% by weight of styrene.

5. A tripolymer made by polymerizing in aqueous emulsion a mixture of monomeric material consisting of from 40 to 85% by weight of vinyl chloride, from 10 to 50% by weight of isooctyl acrylate, and from 5 to 35% by weight of styrene.

ROBERT J. WOLF. ANTHONY A. NICOLAY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,462,422 Plambeck Feb. 22, 1949 FOREIGN PATENTS Number Country Date 835,357 France Sept. 19, 1938 OTHER REFERENCES Chapin et al., article in J. Am. Chem. Soc. 70, 538-542, February 1948.

Rehberg et al., Ind. Eng. Chem, 40, 1429-1433, August 1948. 

2. A TRIPOLYMER MADE BY POLYMERIZING IN AQUEOUS EMULSION A MIXTURE OF MONOMERIC MATERIAL CONSISTING OF FROM 40 TO 85% BY WEIGHT OF VINYL CHLORIDE, 10 TO 50% BY WEIGHT OF ALKYL ACRYLATE IN WHICH THE ALKYL GROUP CONTAINS A TOTAL OF 8 TO 10 CARBON ATOMS, AND POSSESSES A CARBON CHAIN OF 6 TO 10 CARBON ATOMS, AND FROM 5 TO 35% BY WEIGHT OF STYRENE. 